DETAILED ACTION
Application 17/118980, “ELASTIC CROSSLINKED POLYMER-ENCAPSULATED ANODE PARTICLES FOR LITHIUM BATTERIES AND METHOD OF MANUFACTURING”, was filed with the USPTO on 12/11/20.
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
This Office Action on the merits is in response to communication filed on 10/8/25.
Response to Arguments
Applicant’s arguments filed on 10/8/25 have been fully considered, but are moot in view of the new ground(s) of rejection necessitated by amendment.
Claim Rejections - 35 USC § 103
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102 of this title, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
Claims 1, 4-10, 12, 14-19 and 21-23 is/are rejected under 35 U.S.C. 103 as being unpatentable over the combination of Zhamu (US 2019/0319264) and Barker (US 2018/0301696).
Regarding claim 1 and 2, Zhamu teaches a composite particulate for a lithium battery, wherein said composite particulate comprises one or more anode active material particles that are dispersed in a high-elasticity polymer matrix or encapsulated by a high-elasticity polymer shell (“these elastomers can be used to encapsulate particles of an anode active material”, paragraph [0109]), wherein said high-elasticity polymer matrix or shell has a recoverable tensile strain no less than 5%, when measured without an additive or reinforcement dispersed therein (“elastic deformation strain value >5%”, paragraphs [0099]; “an elastomer having a recoverable tensile strain no less than 5%”, paragraph [0013]), and a lithium ion conductivity no less than 10−8 S/cm at room temperature (“the elastomer has a lithium ion conductivity no less than 10−7 S/cm”, paragraph [0099]).
It is noted that Zhamu primarily emphasizes the inventive elastomer being utilized in a cathode active material layer (e.g. see abstract) rather than an anode active material layer as in the claimed invention; however, Zhamu paragraph [0109] teaches that elastomers can be used in the formation of an anode active material layer. Accordingly, an embodiment wherein an elastomer expressly taught by Zhamu for use in a cathode is implicitly taught, or at least obvious to use, as the elastomer of an anode active material layer.
Zhamu does not appear to teach the composite particulate having a diameter of 10 nm to 50 μm.
In the battery art, Barker teaches hard carbon anode active materials (paragraphs [0001, 0013]), which are desirably configured to have a diameter of 5 to 10 μm (paragraph [0033]) for the benefit of facilitating production of batteries having excellent first discharge specific capacity and exhibit high first discharge capacity efficiency (paragraph [0013]).
It would have been obvious to a person having ordinary skill in the art at the time of invention to configure the anode active material particles of Zhamu to have a diameter lying within the range of 10 nm to 50 μm, since anode materials having size within this range have been used to produce batteries having excellent first discharge specific capacity and exhibit high first discharge capacity efficiency as taught by Barker.
Moreover, Zhamu further teaches the encapsulating polymer shell having a thickness of 0.5 to 10 μm, typically 1 nm to 1 μm (abstract, paragraphs [0013]), for the benefit of allowing facile lithium ion transport (paragraph [0171]). Thus, the composite particles comprising the anode active material and the high-elasticity polymer would have a diameter [i.e. the sum of the particle diameter and coating layer thickness] lying within the claimed 10 nm to 50 μm range.
Regarding claim 4, the cited art remains as applied to claim 1. Zhamu does not expressly teach wherein said high-elasticity polymer has a crosslinking ratio from about 0.1% to 70%.
However, Zhamu does teach degree of cross-linking as a result-effective variable, for example, at paragraph [0102] which states, “the network polymer or cross-linked polymer should have a relatively low degree of cross-linking or low cross-link density to impart a high elastic deformation”.
The claimed cross linking range of 0.1% to 70% is found to be prima facie obvious since Zhamu suggests “a relatively low degree of cross-linking” is desirable for promoting high degree of elasticity, and teaches this parameter as a result-effective variable, which the skilled artisan could optimize through experimentation to determine the suitable range.
Regarding claim 5, the cited art remains as applied to claim 1. Zhamu further teaches wherein the high-elasticity polymer contains a cross-linked network of polymer chains, a semi-interpenetrating network, or a simultaneous interpenetrating network of two cross-linked polymer chains (paragraphs [0072, 0106] at least teaches a cross-linked network of polymer chains).
Regarding claim 6-7, the cited art remains as applied to claim 1. Zhamu further teaches wherein said high-elasticity polymer matrix or shell further contains from 0.01% to 30% by weight of a graphite, graphene, or carbon material dispersed therein wherein said graphite, graphene, or carbon material is selected from polymeric carbon, amorphous carbon, chemical vapor deposition carbon, coal tar pitch, petroleum pitch, meso-phase pitch, carbon black, coke, acetylene black, activated carbon, graphite particles, carbon particles, meso-phase microbeads, carbon or graphite fibers, carbon nanotubes, carbon nano-fibers, graphitic nano-fibers, graphene sheets, or a combination thereof and said graphite, graphene, or carbon material forms a 3D network of electron-conducting pathways that are in electronic contacts with said anode material particles (paragraph [0021]).
Regarding claim 8, the cited art remains as applied to claim 1. Zhamu further teaches wherein said anode active material is selected from the group consisting of: (a) silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), phosphorus (P), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), and cadmium (Cd); (b) alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, or Cd with other elements; (c) oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Co, V, or Cd, and their mixtures, composites, or lithium-containing composites; (d) salts and hydroxides of Sn; (e) lithium titanate, lithium manganate, lithium aluminate, lithium titanium niobium oxide, lithium-containing titanium oxide, lithium transition metal oxide, ZnCo.sub.2O.sub.4; (f) carbon or graphite particles (g) prelithiated versions thereof; and (h) combinations thereof (paragraph [0033]).
Regarding claim 9, the cited art remains as applied to claim 1. Zhamu further teaches wherein said anode active material contains a prelithiated Si, prelithiated Ge, prelithiated Sn, prelithiated SnOx, prelithiated SiOx, prelithiated iron oxide, prelithiated V2O5, prelithiated V3O8, prelithiated Co3O4, prelithiated Ni3O4, or a combination thereof, wherein x=1 to 2 (paragraph [0127]).
Regarding claim 10, the cited art remains as applied to claim 1. Zhamu does not appear to teach wherein said anode active material particles or the composite particulate, or both, are porous.
In the battery art, Barker teaches hard carbon anode active materials (paragraphs [0001, 0013]), which are desirably made porous (paragraph [0020]) for the benefit of compensating volume expansion so as to provide improved long-term behavior (paragraph [0020]).
It would have been obvious to a person having ordinary skill in the art at the time of invention to configure the anode active material particles of Zhamu to be porous for the benefit of compensating volume expansion so as to provide improved long-term behavior as taught by Barker.
Regarding claim 12, the cited art remains as applied to claim 1. Zhamu further teaches wherein said high-elasticity polymer has a lithium ion conductivity from 10−6 S/cm to 10−2 S/cm (paragraph [0013]).
Regarding claim 14, the cited art remains as applied to claim 1. Zhamu further teaches wherein said high-elasticity polymer matrix or shell further comprises from 0.1% to 50% by weight of a lithium ion-conducting additive dispersed therein (paragraph [0021]).
Regarding claim 15, the cited art remains as applied to claim 1. Zhamu further teaches wherein said high-elasticity polymer forms a mixture with an elastomer selected from natural polyisoprene, synthetic polyisoprene, polybutadiene, chloroprene rubber, polychloroprene, butyl rubber, styrene-butadiene rubber, nitrile rubber, ethylene propylene rubber, ethylene propylene diene rubber, epichlorohydrin rubber, polyacrylic rubber, silicone rubber, fluorosilicone rubber, perfluoroelastomers, polyether block amides, chlorosulfonated polyethylene, ethylene-vinyl acetate, thermoplastic elastomer, protein resilin, protein elastin, ethylene oxide-epichlorohydrin copolymer, polyurethane, urethane-urea copolymer, or a combination thereof (paragraph [0015]).
Regarding claim 16, the cited art remains as applied to claim 1. Zhamu further teaches wherein said high-elasticity polymer contains a lithium ion-conducting additive dispersed therein wherein said lithium ion-conducting additive is selected from Li2CO3, Li2O, Li2C2O4, LiOH, LiX, ROCO2Li, HCOLi, ROLi, (ROCO2Li)2, (CH2OCO2Li)2, Li2S, LixSOy, or a combination thereof, wherein X=F, Cl, I, or Br, R=a hydrocarbon group, 0<x≤1, 1≤y≤4 (paragraph [0022]).
Regarding claim 17, the cited art remains as applied to claim 1. Zhamu further teaches wherein said high-elasticity polymer contains a lithium ion-conducting additive dispersed therein and said additive is selected lithium perchlorate (LiClO4), lithium hexafluorophosphate (LiPF6), lithium borofluoride (LiBF4), lithium hexafluoroarsenide (LiAsF6), lithium trifluoro-methanesulfonate (LiCF3SO3), bis-trifluoromethyl sulfonylimide lithium (LiN(CF3SO2)2), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF2C2O4), lithium nitrate (LiNO3), Li-fluoroalkyl-phosphate (LiPF3(CF2CF3)3), lithium bisperfluoro-ethylsulfonylimide (LiBETI), lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium trifluoromethanesulfonimide (LiTFSI), an ionic liquid-based lithium salt, or a combination thereof (paragraph [0023]).
Regarding claim 18, the cited art remains as applied to claim 1. Zhamu further teaches wherein said high-elasticity polymer is mixed with an electron-conducting polymer selected from polyaniline, polypyrrole, polythiophene, polyfuran, a bi-cyclic polymer, a sulfonated derivative thereof, or a combination thereof (paragraph [0026]).
Regarding claim 19, the cited art remains as applied to claim 1. Zhamu further teaches wherein the high-elasticity polymer forms a mixture or blend with a lithium ion-conducting polymer selected from poly(ethylene oxide) (PEO), Polypropylene oxide (PPO), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVdF), Poly bis-methoxy ethoxyethoxide-phosphazenex, Polyvinyl chloride, Polydimethylsiloxane, poly(vinylidene fluoride)-hexafluoropropylene (PVDF-HFP), a sulfonated derivative thereof, or a combination thereof (paragraph [0027]).
Regarding claim 21, the cited art remains as applied to claim 1. Zhamu further teaches an anode comprising anode active material particles and an elastomer (paragraph [0109]), wherein the elastomer may comprise conductive additive (paragraph [0021]), but does not expressly teach that the anode comprises the anode material, a conductive additive, and a binder resin to bind the constituents together.
However, Zhamu does teach such conductive additives and binders as part of a typical electrode layer, specifically a cathode layer (paragraphs [0041-0042, 0058]).
Moreover, in the battery art, Barker teaches that functioning anodes may comprise active material, conductive carbon, and binder (paragraph [0137]).
It would have been obvious to a person having ordinary skill in the art to form the anode using the previously mentioned anode active material particles and elastomer, and further to include conductive additive to improve electrical conductivity, and binder to improve adhesion amongst the components, for the benefit of providing a functional anode as taught by Barker.
Regarding claim 22-23, the cited art remains as applied to claim 21. Zhamu further teaches the anode as a subcomponent of a lithium battery further comprising a cathode, a separator, and an electrolyte in ionic contact with said anode and said cathode, wherein the lithium battery is a lithium-selenium battery (e.g. paragraph [0013]).
Claims 2 is/are rejected under 35 U.S.C. 103 as being unpatentable over the combination of Zhamu (US 2019/0319264), Barker (US 2018/0301696) and Hong (US 2018/0294518).
Regarding claim 2, the cited art remains as applied to claim 1. Zhamu does not appear to teach wherein the high-elasticity polymer comprises poly(acrylic acid) and poly(vinyl alcohol) chains.
In the battery art, Hong teaches a polymer film which coats and integrates with an active material (paragraph [0043]), wherein the polymer film is configured to have high flexibility and ionic conductivity (paragraphs [0008, 0003]) and is formed from a polymer network comprising polyacrylic acid and polyvinyl alcohol chains (abstract, paragraph [0011])
It would have been obvious to a person having ordinary skill in the art at the time of invention to include a crosslinked network of polyacrylic acid and polyvinyl alcohol chains in the high-elasticity polymer for the benefit of attaining desirable flexibility and ionic conductivity as taught by Hong.
Claims 3 is/are rejected under 35 U.S.C. 103 as being unpatentable over the combination of Zhamu (US 2019/0319264) and Barker (US 2018/0301696) and Wood (WO 2017/160892).
Regarding independent claim 3, the cited art remains as applied to claim 1. Zhamu further teaches that the polymer may comprise a cross-linking agent (paragraph [0043, 0105]), but does not appear to teach that the high elasticity polymer may comprise the both of poly(acrylic acid) and glycerol.
In the battery art, Wood teaches that a polymer dispersion may be gelled by using polyacrylic acid as a hydrogen bonding component and glycerol as a cross-linking agent (paragraphs [0022-0023]).
It would have been obvious to a person having ordinary skill in the art at the time of invention to include both poly(acrylic acid) and glycerol in the polymer since these compounds may be used together to provide the cross-linking agent to facilitate the polymerization process as taught by Wood.
Claims 11, 13 and 20 is/are rejected under 35 U.S.C. 103 as being unpatentable over the combination of Zhamu (US 2019/0319264), Barker (US 2018/0301696), Pan (US 2019/0280301) and Zhamu’262 (US 2019/0319262).
Regarding claim 11 and 13, the cited art remains as applied to claim 1. Zhamu further teaches (e.g. Figure 4) wherein one or more of said cathode active material particles (e.g. item 24) is coated/encapsulated with a layer/shell of carbon or graphene (item 26) disposed between said one or more particles and said high-elasticity polymer matrix (item 28), but does not expressly teach anode particles coated with a layer of carbon or graphene disposed between said one or more particles and said high-elasticity polymer matrix or wherein the composite particulate [including the anode active material particle and an elastomeric polymer matrix or polymer shell] is further coated or encapsulated by a shell of conducting material which is a conducting composite.
In the battery art, Pan teaches providing anode particles with a conductive coating either directly on the un-encapsulated anode particles, or onto encapsulated anode particles (paragraph [0027]; see also Figure 4 and “anode active material particles 24 (e.g. Si nanoparticles) coated with a conductive protection layer 26” at paragraph [0089]). Pan further teaches that such a carbon layer is one form of conductive protection coating layers, with exemplary species of the conductive protecting material including a carbon material, an electronically conductive polymer, a conductive metal oxide, and a conductive metal (paragraph [0029]).
Furthermore, regarding claim 13, in the battery art Zhamu’262 teaches that a polymer protection layer may be formed from a polymer containing an electrically conductive material dispersed therein (paragraph [0024]; Zhamu’262 claim 4)
It would have been obvious to a person having ordinary skill in the art at the time of invention to modify the invention of Zhamu by providing a conductive protecting layer either directly on the anode active material particles, or on the elastomer-encapsulated anode active material particulate, for the benefit of providing additional protection and electronic conduction to the particles as taught by Pan. Moreover, it would have been obvious to form the protective layer from a carbon layer as in claim 11, or a conducting composite layer [e.g. an electronically conducting polymer which could be formed as a composite of polymer having electrically conductive material dispersed therein] as in claim 13, as both of these materials are useful as protective conducting layers as taught by Pan in view of Zhamu’262.
Regarding claim 20, the cited art remains as applied to claim 1. Zhamu further teaches wherein said anode active material is lithiated to contain from 0.1% to 54.7% by weight of lithium.
In the battery art, Pan teaches that an anode active material may be pre-intercalated by or doped with lithium ions up to a weight fraction from 0.1% to 54.7% of Li in the lithiated product (paragraph [0025]).
It would have been obvious to a person having ordinary skill in the art at the time of invention to lithiate the anode active material to contain from 0.1% to 54.7% by weight of lithium as taught by Pan for the benefit of providing extra lithium ions to faciliate charge-discharge energy storage.
Conclusion
Applicant's amendment necessitated the new ground(s) of rejection presented in this Office action. Accordingly, THIS ACTION IS MADE FINAL. See MPEP § 706.07(a). Applicant is reminded of the extension of time policy as set forth in 37 CFR 1.136(a).
A shortened statutory period for reply to this final action is set to expire THREE MONTHS from the mailing date of this action. In the event a first reply is filed within TWO MONTHS of the mailing date of this final action and the advisory action is not mailed until after the end of the THREE-MONTH shortened statutory period, then the shortened statutory period will expire on the date the advisory action is mailed, and any nonprovisional extension fee (37 CFR 1.17(a)) pursuant to 37 CFR 1.136(a) will be calculated from the mailing date of the advisory action. In no event, however, will the statutory period for reply expire later than SIX MONTHS from the mailing date of this final action.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to JEREMIAH R SMITH whose telephone number is (571)270-7005. The examiner can normally be reached on Mon-Fri: 9 AM-5 PM (EST).
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/JEREMIAH R SMITH/Primary Examiner, Art Unit 1723